Production of pattern effects upon textile fabrics or other materials



ment of fabricsor other materials made of or' Patented Aug. 15, 1933 A UNITE-D. s ri- E5 PRODUCTION OF PATTERN EFFECTS UPON I TEXTILE FABRICS 0a OTHER MATE PJALS George Holland Ellis, Spondon, near- Derby, England, assignor to Celanese Corporation of America, a Corporation of Delaware No Drawing. Application September 10, 1929, Serial No. 391,692, andinzGreat/Britain; Sep* tember 29, 1928 8 Claims.

This invention relates to a new process forthe newprocess being of particular valuein thetreatcontaining cellulose acetate or other organic esters of cellulose or made of or containing cellulose others."

According to the new process of the present invention, in the production of azo colouring matters on textile fabrics or other materials by diazotizing amines or amino colouring matters on the material and developing, discharge or resist effects are produced by treating the materials locally before diazotization and development so as to render the amines or amino colouring matters in selected areas incapableof forming colouring matters by diazotization and development. The developer components may be applied before the diazotization, for example together with the amines or amino colouring matters, so that upon diazotization development is effected simultaneously.

I have found that chlorates, chromates or other oxidizing discharges may beapplied to the materialsso as to render amines oramino colouring matters incapable of forming colouring matters by diazotization and development. Such a treatment of amines or amino colouring matters is entirely novel and constitutes a remarkable and valuable advance in the art of discharge printing.

On account of the ease with which amines may be incorporated in cellulose esters and ethers the processes of the invention are of particular value as applied to materials containing such cellulose. derivatives. The invention is however applicableto the discharge of amino colouring matters and to the production of the pattern effects upon materials other than cellulose derivatives.

As examples of amino bases and amino colouring matters on the one hand, and developers or coupling components on the other hand, which may be used forthe purpose of the present invention, the following may be instanced, though the listing of these examples implies no limitation of the invention thereto.

Amino bases and amino colouring matters Metanitraniline Paranitraniline. Paranitroorthotoluidine Metanitroparatoluidine Paranitroorthoanisidine. Met'anitroorthoanisidine Aminoaaobenzene Aminoazotoluene production of pattern ordischarge or resist effects upon textilefabrics or other materials, the

Paraaminobenzeneazodimethylaniline Paraaminobenzeneazoalphanaphthylamine Orthomethoxybenzeneazoalphanaphthylamine Dimethylaminobenzeneazoalphanaphthylamine Benzidine Tolidine Dianisidine Diaminodiphenylmethane Diazam-ine Bordeaux B -(Sandoz.)

Chlorazol black BH- (Colour Index No. 401) Developers or coupling components 7 Xylidines, cresidines, anisidines, phenetidines,

metatoluidine, metaphenylenediamine; nitrometaphenylenediamine, alkyl-, aryl-= or-aralkylan-ilines, phenols, cresols, resorcinol, aminophenolst or alkylamino-phenols, such as dimethylmetaaminophenol, a-OI p-naphthylamines or -alkylderivatives thereof, 1 ornaphthylamine others, w-oxy-ethyl-a-naphthylamine, 7-Chl0I-{3- oxy-propyl-a-naphthylamine, (condensation of a-naphthylamine and epichlorhydrin), aminonaphthoic acids, amino-naphtholsaor any compounds obtained by the acetylation or other acidylation of amino-groups in the said coupling components. r 1

The aminoazo colouring matters to be used for-discharge purposes according to the present invention may of course be applied as such or they may. be produced on the material itself before the application of the discharge.

As oxidation discharges we find that chlorates ormixtures of .chlorates and ohromates. give the best results. Any chlorates, for. example alkali chlorates, such as sodium or potassium chlorate,

I or chlorates of other bases, for instance alumina,

may beuemployed, preferably in' conjunction with accelerators cor. catalysts, for example. salts of iron, e. g. prussiates, or salts of vanadium. Assistants, for instance tartaric acid, citric acid, so.- dium citrate and the like, may also be, employed.

The concentration of the discharges and the consoluble in oils, soaps, fats or the like), of the mineral pigment type and vat dyes of the an thraquinone series, e. g. m-nitraniline Naphthol AS (c-hydroxy naphthoic acid anilide) p nitraniline- [i-naphthol or Naphthol AS, pnitro-o-toluidine fl-naphthol or Naphthol AS, and p nit'roo-anisidine c-naphthol or N aphthol AS, Methylene blue (Color Index No. 922) Rhodamine 6 G extra (color Index llo. 152), Chrome yellow (Color Index No. 1270), Chrome ycllow, Guignets green (Color Index No. 1292), and Vermilion (Color Index No. 1280). The vat dyestuffs of the anthraquinone series maybe incorporated in the pastes or other compositions in the form of esters of their leuco compounds, while the mineral pigmentcolours may be applied in conjunction with albumens or'the like. Many of the colouring matters commonly used for the colouration of. cellulose ester materials, particularly colouring matters of the nitro-oliarylamine series or of the amino anthraquinone series, may likewise be used. Care should be exercised, however, in the choice of dyestuffs of the u-amino anthraquinone series since some members of this class having a substituent, particularly hydroxyl or amino, in the para position to the a-amino group or insuiiiciently resistant to the action of oxidizing discharge preparations.

It has further been found that the acidylaminoanthraquinone colouring matters, owing to their resistance to theaction of oxidizing agents, are particularly useful for incorporation in oxidizing discharge preparations, whether these preparations contain chloratcs. or-chromates or any other oxidation discharges. The acidylamino-anthrm. quinones. may'contain in addition toacidylamino groups other substituent groups or atoms, such as hydroxy groups, alkoxy groups and halogen.

atoms, Of this group of'colouring matters the aliphatic acidylainino-anthraquinones especial interest for-use in coloured discharge preparations owing to their good aillnity for cellulose ester and ether materials. The following are examples of such aliphatic acidylamino anthraquinones and the colourations yielded by them on cellulose esters and ethers:--

l-acetylamino-anthraquinone; Yellow 1:4-di-(propidnylamino) anthraquinone Red l-methylaniinol-acetylamino anthraquinone Reddish violet 1 4= di- (acetylethylarnine) anthraquinone Red 1 5-di- (acetylamino) A S-dihydroxyanthraquinone Red l-propionylmethylamino i; 5-dihydroxyv anthraquinone Red 1 i-di- (acetylinethylamino) -5 6 -dihydroxy-anthraquinone Violet 2 -propionylamino-anthra- .quinone Pale greenish yellow As indicated above the developer may be ap-: plied to the fibre together with the amino base or the like beforethe local application of the discharging agent, the final development being by are of means of nitrous acid. The materials before treatment with nitrous acid are preferably dried and aged or steamed. I

The discharge effects may be obtained with 7 any suitable means of local application, for example machine or hand-block printing, spraying, stencilling or the like.

As indicated above the most valuable results may be obtained according to the present invention onl naterials containing organic esters of cellulose, for example cellulose acetate, cellulose formate, propionate or butyrate, or the products obtained by the treatment of alkalized cellulose with esterifying agents (e. g. the product known as immunized cotton obtained with para-tolugoods containing, for example, cellulose acetate or other cellulose esters and/or ethers in association with other fibres, for instance cotton or the cellulosic type of artificial silk. Furthermore, such mixed goods may be dyed differentially by utilizing the property of the cellulose ester portion of absorbing amines substantively from so lution, in preference to their absorption by the other components. Dillerential or uniform shades may be obtained by means of colours having an ailinity for the non-ester portion but which resist cellulose esters. According to the effect desired, such. colouring matter for the nones ter portion of the, mixed goods may be so chosen that they are either discharged by'or resist the discharging agents employed; further they may if desired be selected so that they either resist or respond to the diazotization and development operations.

The following examples are intended to illustrate the invention but not to limit it in any way:-

- Example 1 A fabric composed of cellulose acetate yarns is treated in a bath of volume ratio :1 with 0.5% of its weight of para nitro-ortho-anisidine, previously dispersed by heating with sodium sulphoricinoleate. ceed for 1 hours at C. after which the fabric is washed and dried at a low temperature and further prepared for printing as desired. It is then printed by roller printing machine with a paste composed as follows:

soc 190 grams grams grams After printing the material is dried and steamed in the cottage steamer for 15 minutes with steam at 5 lbs. pressure after which it is diazotized for half an hour in a cold 50:1 bath containing 5% of its weight of sodium nitrite and 16% of its weight of hydrochloric acid 28 Tw..

The dyeing is allowed to pro- Car When diazotization is complete the fabric is washed well in cold water and developed with 2% of its weight of betaoxynaphthoic acid, after which it is rinsed, soaped lightly and otherwise treated and finished as desired or requisite. A white pattern is thus obtained on a deep pink ground.

' Example 2 A fabric composed of cellulose acetate yarns is treated in a bath of volume ratio 50:1 containing 1% of its weight of dianisidine dispersed prior to adding to the dyebath in sodium sulphoricinoleate. After treating at 80 C. for 1 hours the fabric is washed and dried and further prepared for printing as desired. It is then printed by a roller printing machine with a paste composed as follows:-

500 grams gum arabic 1 :1 190 grams aluminium sulphate 1:1 90 grams sodium chlorate cryst: {120 grams water 25 grams potassium ferricyanide {'75 grams water After printing the material is dried and steamed in the cottage steamer for 3 minutes with steam at 5 lbs. pressure, or given an equivalent steaming in the rapid ager, after which it is diazotized for half an hour in a cold 50:1 bath containing 5% of its weight of sodium nitrite and 16% of its weight of hydrochloric acid 28 Tw. After diazotization the material is well washed in cold water and developed by known methods with 3% of its weight of betaoxynaphthoic acid. It is then rinsed, soaped lightly and otherwise treated and finished as desired or requisite.

The unprinted portions are deep blue and the printed portions discharged.

Example 3 A fabric composed of cellulose acetate yarns is treated in a bath of volume ratio 50:1 with 0.5% of its weight of aminoazotoluene sulphate, rendered slightly alkaline with ammonia after dissolving. The dyeing is continued for 1%; hours at 80 C. and the fabric is then washed and dried at a low temperature and further prepared for printing as desired. It is then printed by roller printing machine or hand-block with a paste consisting of the following:

500 grams gum arabic 1:1 190 grams aluminium sulphate 1:1 90 grams sodium chlorate cryst: {120 grams water 25 grams potassium ferricyanide grams water After printing, the material is dried and steamed in the cottage steamer for 15 minutes at 5 lbs. pressure, after which it is diazotized in a bath containing 5% of its Weight of sodium nitrite and 16% of its weight of hydrochloric acid of 28 Tw strength. After diazotizing for hour the fabric is washed well in cold water and developed in known manner with 2% of its weight of betaoxynaphthoic acid. It is finally rinsed, soaped lightly and otherwise treated and finished as desired or requisite. A white pattern on a bluish red ground is thus obtained.

then treated cold for 1 hours in a bath' con- Example 4 f A fabric, woven from cellulose acetate yarns is dyed ina mixture of 0.5% of o.methoxybenzeneazoalphanaphthylarnine and 1% of Naphthol 8O AS.BS, calculated 'onthe weight of material. (The Naphthol AS.BS' is dissolved in aqueous caustic soda and poured into the dyebath prepared with 2 ccs. of sodium sulphoricinoleate per litre. The bath is now just neutralized with dilute acetic acid and the solution of the above amine, previously dispersed by heating with aqueous sodium sulphoricinoleate, added.) Dyeing is continued for 1 hours at C. and the inaterial well washed, dried and otherwise. prepared for printing as desired. It is then printed with a paste composed as follows:-

, a After printing and drying, the material is given a very short steaming, e. g'. 2 minutes in the cottage steamer at 3 lbs. pressure or an equivalent steaming in the continuous ager. The fabric is 1 taining 4 grams per litre of sodium nitrite and 05 6 grams per litre of acetic acid, after which it is rinsed and soaped and otherwise treated as desired or requisite. The result is a tinted discharge on a navy blue ground. 1

Example 5 A fabric composed of cellulose acetate yarns is treated, as in dyeing, with 1% of its weight of dianisidine, the latter being dispersed by heat- 5 ing with three times its weight of aqueous sodium sulphoricinoleate before being added to the bath. The treatment is continued for 1 hours at 80 C. the material being then washed well,

dried and prepared for printing as desired. It

is then printed by roller printing machine with a paste of the following composition:-

After printing the materialis dried and steamed in the cottage steamer for 3 minutes with steam at 5 lbs. or given an equivalent steaming in the rapid ager at 100 C. After steaming the fabric is diazotized for 20 minutes in the cold in a bath containing 2% of sodium nitrite and 7% of hydrochloric acid 28 Tw. calculated on the weight of the material. After diazotization is complete the fabric is washed well in cold water and de veloped in known manner with 1% of its weight of betaoxynaphthoic acid, after which it is rinsed, soaped lightly and otherwise treated as desired or requisite. The result is a greenish tinted discharge on a deep blue ground.

What I claim and desire to secure by Letters Patent is:-

1. Process for the production of discharge effects on materials, comprising applying a diazotizable amino compound to a material comprising an organic derivative of cellulose,- applying to the material locally an oxidizing discharge and treating' the amino compound so that it is rendered incapable of diazotization in the selected areas, and finally diazotizing and developing.

2. Process for the production of discharge ef fects on materials, comprising applying a diazotizable amino compound to'a' material comprising cellulose acetate, applying to the material locally an oxidizing discharge and treating the amino compound so that it is rendered incapable of diazotizationin the selected areas, and finally diazotizing and developing. I f

3. Process for the production of discharge effects on materials, comprising applying a diazotizable amino compound to a material comprising an organic derivative of cellulose, applying to the material locally a chlorate discharge and treating the amino compound so that it is rendered incapable of diazotization in the selected areas, and finally diazotizing and developing. c

4. Process for the production of discharge effects on materials, comprising applying a. diazotizable amino compound to a material comprising cellulose acetate, applying to the mate-.

rial locally a chlorate discharge and treating the amino compound so that it is rendered incapable of diazotization in the selected areas, and finally diazotizing and developing.

5. Process for the production of discharge effects on materials, comprising applying a di azotizable amino compound to a material comprising an organic derivativeof cellulose, apply-' ing to the material locally an oxidizing discharge, drying and ageing to render the amino compound incapable of diazotization in the selected areas, and finally diazotizing and developing.

1 6.v Process for the production of discharge effects on materials comprising applying' a azotizable amino compound to a material comprising cellulose acetate, applying to the material-locally an oxidizing discharge, drying and ageing to render the amine compound incapable of diazotization in the selected areas, and finally diazotizing and developing.

7. Process for the production of discharge effects on materials, comprising applying a diazotizable amino compound together with a developer component to a material comprising an organic derivative of cellulose, applying to the material locally an oxidizing discharge and treating the amino compound so that it is rendered incapable of diazotization in the selected areas, and finally diazotizing.

8. Process for the production of discharge effects on materials, comprising applying-a diazotizable amino compound together with a developer component to a material comprising cellulose acetate, applying to the material locally an oxidizing discharge and treating the amino compound so that it is rendered incapable of diazotization in the selected areas, and finally diazotizing.

' GEORGE HOLLAND ELLIS. 

